Zirconium based coating composition and production of zirconium oxide-coated graphite formed article

[Detailed Description of the Invention]

(Field of the Invention) The present invention can be saved for a long period of time, can be coated easily, and relates to the zircon system coating constituent in which the coat excellent in stability is obtained. The present invention relates to the method of manufacturing easily the zircon system oxide covering black lead fabrication object which has the coat excellent in stability further, and hanging it. (PRIOR ART) In order to raise the corrosion resistance, heat resistance, abrasion resistance, insulation, etc. on materials, such as metal, a plastic, wood, paper, cement, and black lead, conventionally, Forming a coat by coating is performed and a zircon system constituent is especially excellent in corrosion resistance, heat resistance, abrasion resistance, insulation, etc., and also since the coefficient of thermal expansion is low, it is useful as a coating constituent for the above-mentioned material. A zircon system constituent is in JP,61-250063,A, for example, the constituent which comes out and mixes formula Zr(QCs) l, 1, the zirconium compound expressed, ethyl silicate, and isopropyl alcohol is indicated In JP,63-190175,A, the constituent consisting of zirconium oxy acid salt, silicon Alkoxide or its derivative, water, and an organic solvent is described. However, the above-mentioned constituent had bad preservation stability over a long period of time, and the coat produced by moreover applying on a substrate had the fault of being easy to produce a crack and exfoliation. On the other hand, among the above-mentioned materials, a coefficient of thermal expansion is known as a material which was low excellent in heat-resistant shock nature, and black lead is especially used as a material of the jig for using it under high temperature. However, black lead has the fault of being inferior to the oxidation resistance in high temperature. in using the jig of black lead as an object for powder metallurgy, alumina powder is sprinkled to a graphite surface, or Caking agents, such as an alumina system and a silica system, are applied to it, and it receives black lead of fusion metal -- although it gets wet and it is necessary to prevent And reaction A former method has the fault of a process being complicated and also worsening work environment with alumina fine powder. A Caking agent exfoliated easily from a graphite surface according to a difference of a coefficient of thermal expansion of a Caking agent and black lead, and also under a hydrogen atmosphere, silica and hydrogen in a Caking agent reacted in high temperature, vapor was generated, and a latter method had the fault of barring metaled sintering. In order to solve the above-mentioned fault, forming covering of a zircon system constituent in the surface of a black lead fabrication object is proposed. As this covering formation method, although the vapor-depositing method, the sputtering method, a CVD method, a thermal-spraying method, a paste sintering process, a coat thermal decomposition method, etc. were known, it was difficult to form a thick film of 0.1 micrometer or more, and these methods were insufficient for preventing oxidization degradation of black lead etc. In JP,1-122982,A, it is tetra-alkoxysilane, An application or a method of drying [ is impregnated and ] and covering is indicated on a black lead fabrication object in solution, such as the hydrolysis thing and/or a partial condensation thing, Zirconium tetraalkoxide, its hydrolysis thing, and/or a partial condensation thing. A coat obtained with a described method has a coefficient of thermal expansion almost comparable as black lead, to this coat, Melting-metal shows neither wettability nor reactivity and a coat does not react to hydrogen. However, since it was easy to hydrolyze coating liquid, the described method had the fault that it could not save for a long time. And there was a fault of the stability of the coat obtained having been bad and being easy to produce a crack and exfoliation. (Object of the Invention) It is made in view of the above-mentioned fault, and the present invention is the object, Coating can be done easily, and while providing the zircon system coating constituent in which the coat excellent in stability is obtained and in which long-term preservation is possible, it is in providing the manufacturing method of zircon system oxide covering black lead using the coating constituent. (Means for solving problem) Although Zirconium tetraalkoxide (a) used by the present invention is a compound denoted by general formula Zr4 (OR') and R1 shows an aliphatic hydrocarbon machine among a formula, Since the stability of a zircon system coating constituent will fall and preservability will worsen over a long period of time if a carbon number increases, a carbon number is limited to 1~5. As the above-mentioned Zirconium tetraalkoxide (a), For example, Zirconium tetramethoxide, Zirconium tetraethoxide, zirconium tetra 1so-propoxide, zirconium tetra n-butoxide, zirconium tetra 8eC-butoxide, zirconium tetra tert-butoxide, etc. are raised, and zirconium tetra n-butoxide and zirconium tetra 1so-propoxide are especially preferred. These may be used alone and may be used together two or more sorts. Although the tetra-alkoxysilane (b) used by the present invention is a compound denoted by general formula 5i(OR")+ and R2 shows an aliphatic hydrocarbon machine among a formula, Since the stability of a zircon system coating constituent will fall and preservability will worsen over a long period of time if a carbon number increases, a carbon number is limited to 1~5. As the above-mentioned tetra-alkoxysilane (b), For example, tetra-methoxysilane, tetra-ethoxy Silane, tetra n-propoxysilane, Tetra 1so-propoxysilane, tetra n-butoxysilane, tetra se The leaves dibutoxysilane tetra tert-butoxysilane, etc. are raised, and tetra-ethoxy Silane and tetra-methoxysilane are especially preferred. These may be used alone and may be used together two or more sorts. The amount of addition to Zirconium tetraalkoxide (a) of the above-mentioned tetra-alkoxysilane (b) decreases. The stability of a zircon system coating constituent falls and preservability is wrong (since it will become easy to produce a crack in the coat obtained if it increases, tetra-alkoxysilane (b) / Zirconium tetraalkoxide (a), and a (molar ratio) are limited to 0.25~2.5.) over a long period of time. As beta-Diketone (c) used for the present invention, For example, Acetyl acetone, benzoyl acetone, dibenzo Il methane, Dipivaloyl methane, 3-methyl pentane 2, 4-dione, trifluoroacetyl acetone, benzoyltrifluoroacetone, etc. are raised, and Acetyl acetone and benzoyl acetone are especially preferred. These may be used alone and may be used together two or more sorts. The amount of addition to Zirconium tetraalkoxide (a) of the above-mentioned beta-Diketone (c), Since it becomes easy to produce a crack in the coat which the stability of a zircon system coating constituent will fall and preservability will worsen over a long period of time if it decreases, and will be obtained if it increases, beta-Diketone (c) / Zirconium tetraalkoxide (a), and a (molar ratio) are limited to 0.5~6. The organic solvent (d) used for the present invention is the above-mentioned Zirconium tetraalkoxide (a+m not being what will be limited especially if it calls and there are tetra-alkoxysilane (b), (it being hereafter called all the Alkoxide), and compatibility). For example, ketone, such as alcohols, such as methyl alcohol, ethyl alcohol, isopropyl alcohol, and butyl alcohol, acetone, and methyl ethyl ketone, benzene, toluene, etc. are raised, and especially isopropyl alcohol is preferred. These may be used alone and may be used together two or more sorts. The amount of addition to all the Alkoxide of the above-mentioned organic solvent (d), Since it becomes easy to produce a pinhole in the coat which the stability of a zircon system coating constituent will fall and preservability will worsen over a long period of time if it decreases, and will be obtained if it increases, organic solvent (d) / all the Alkoxide (molar ratio) are limited to 0.05~500, and are 0.2~300 preferably. The amount of addition to all the Alkoxide of the water (e) used by the present invention, Since the stability of a zircon system coating constituent will fall and preservability will worsen over a long period of time if it becomes easy to produce a crack in the coat which will be obtained if it decreases and it increases in it, water (e) / all the Alkoxide (molar ratio) are limited to 0.02~2. As a catalyst for promoting hydrolysis of all the Alkoxide in the above-mentioned water (e), it is preferred that acid or a base is added. As the above-mentioned acid, organic acid, such as inorganic acid, such as chloride, fluoric acid, and nitric acid, acetic acid, and formic acid, is raised, ammonia, sodium hydroxide, a potassium hydrate, etc. are raised as a base, for example, and especially chloride is preferred. As for the above-mentioned acid or the amount of addition of a base, since there is no facilitatory effect of hydrolysis, the stability of a zircon system coating constituent will fall and preservability will worsen over a long period of time if it increases if it decreases, 0.01~15 mol is preferred to water 11. The zircon system coating constituent of the present invention is obtained by mixing each component mentioned above, Although it is not limited, after especially the mixing method mixes the above-mentioned Zirconium tetraalkoxide (a), beta-Diketone (c), and an organic solvent (d), it is preferred to add the above-mentioned tetra-alkoxysilane (b) and water (e). Zircon powder may be added by the zircon system coating constituent of the present invention in order to further raise the stability (crack resistance, fissility-proof, etc.) of the coat obtained. Since it becomes easy to generate a crack in the coat which will be obtained if distribution into a zircon system coating constituent will become difficult if it becomes small, and it becomes large, as for the average particle diameter of the above-mentioned zircon powder, 0 and 01~100 micrometers are preferred, and especially its 0.02~2 micrometers are preferred. The amount of addition to the inside of the zircon system coating constituent of the above-mentioned zircon powder, Since the degree of improvement in the stability of the coat which will be obtained if it decreases becomes low, the stability of a zircon system coating constituent will fall and preservability will worsen over a long period of time, if it increases, 1~60 % of the weight is preferred among all the zircon system oxides (total quantity of the oxide formed from Zirconium tetraalkoxide (a) and tetra-alkoxysilane (b), and zircon powder). As for addition of zircon powder, it is preferred to be made after carrying out mixed churning of each component of the above-mentioned zircon system coating constituent. It is applied or impregnated, the zircon system coating constituent mentioned above is dried by the black lead fabrication object, and a zircon system oxide is covered with the manufacturing method of the zircon system oxide covering black lead fabrication object of present invention 2. The methods that the manufacturing method of the above-mentioned black lead fabrication object is arbitrary may be adopted. For example, after using natural graphite, artificial black lead, etc. as a starting material and fabricating them by extrusion molding, notes die forming, etc., After fabricating by extrusion molding, notes die forming, etc. by using the thing of quality of amorphous carbon, such as the method and anthracite to calcinate, coal corks, petroleum coke, pitch coke, and carbon black, as a starting material, it calcinates and also the method of graphitizing, etc. are raised. Other type materials, such as clay and metal, may contain in the above-mentioned black lead fabrication inside of the body. It is not limited especially as shape of the above-mentioned black lead fabrication object, and a cylinder, tabular, the letter of a block, the shape of a roll, the shape of a crucible, etc. are raised, for example. It is not limited especially as the above-mentioned coating method, and the coating method by brush, spray coat, dip coat, a spin code, a roll coat, etc. is raised, for example. A method which is not limited especially as the above-mentioned impregnation method, and carries out being immersion impregnated under normal pressure, for example, It is preferred for the method of carrying out to be immersion impregnated under decompression, etc. to be raised, and to carry out to be immersion impregnated under decompression, and it is the degree of decompression, If it becomes low, a zircon system coating constituent will become being hard to be impregnated inside the fine pores of a black lead fabrication object, Since volatilization of a zircon system coating constituent will become intense and a zircon system coating constituent will become solution viscosity rising and being hard to be impregnated inside the fine pores of a black lead fabrication object if it becomes high, I X 10'-3~100Torr is preferred. It is not limited especially as the above-mentioned drying method, and natural seasoning is carried out at the method and room temperature which carry out high temperature heat-treatment after carrying out natural seasoning at the method and room temperature which carry out drying by heating after carrying out natural seasoning for example, at the method and room temperature which carry out natural seasoning at room temperature, and after carrying out drying by heating, the method of carrying out high temperature heat-treatment, etc. are raised. Although the conditions in each stage in the above-mentioned drying method are suitably determined according to the kind of a zircon system coating constituent and black lead fabrication object, As for the natural seasoning in room temperature, it is preferred to carry out for 2~48 hours, as for drying by heating, it is preferred to carry out by 60~300 degreeC for 30 minute~48 hours, and, as for high temperature heat-treatment, it is preferred under non-oxidizing atmosphere to carry out by 450~1700 degreeC for 30 minute~10 hours. (EXAMPLE) Hereinafter, a detailed description of the invention is carried out. The valuation method of each physical properties about the zircon system coating constituent and zircon system oxide covering black lead fabrication object which were shown in the result is as follows. Physical properties about 1 and a zircon system coating constituent (to inside of an initial adhesion [ of +> ] profitable Was done zircon system coating constituent) The slide glass (made by Matsunami) cleaned ultrasonically with acetone is immersed, After pulling up the speed for 300-mm/, it dries under the following conditions, a zircon system oxide enveloping layer is formed, and an evaluation sample is produced, The crosscut tape friction test was done according to JIS D 0202, and the ratio (exfoliation rate) of eye a measure of the zircon system oxide layer [ a measure / of 100 zircon system oxide enveloping layers ] which exfoliated was measured and evaluated. (Dry conditions) Initial dryness: 25degreeC, 24 hours Last dry 2500degreeC (it is Temperature rising at 25degreeC to 50-degreeC/hr) and the zircon system coating constituent which was obtained as for 2-hour (2) boiling water resistance (crack resistance and adhesion endurance) are used, After the evaluation sample produced the same with having evaluated the above-mentioned initial adhesion nature was immersed in boil underwater for 8 hours, the organoleptic test of the state of the surface was conducted, and the following judging standard estimated crack resistance. (Judging standard) O : with no both-sides side crack X: They are those with a crack to the surface. After conducting the above-mentioned organoleptic test, the crosscut tape friction test was done the same with having evaluated the above-mentioned initial adhesion nature, and the exfoliation rate estimated adhesion endurance. (3) The zircon system coating constituent which was obtained as for acid resistance (crack resistance and adhesion endurance) is used, After the evaluation sample produced the same with having evaluated the above-mentioned initial adhesion nature was immersed into 20wt% of chloride for 75 hours, the organoleptic test of the state of the surface was conducted, and the following judging standard estimated crack resistance. (Judging standard) O :-both-sides-side-crack-less x : they are those with a crack to the surface. After conducting the above-mentioned organoleptic test, the crosscut tape friction test was done the same with having evaluated the above-mentioned initial adhesion nature, and the exfoliation rate estimated adhesion endurance. (4) Long-term preservability The crosscut tape friction test was done the same with having evaluated the above-mentioned initial adhesion nature for the hermetic container in which the obtained zircon system coating constituent was enclosed, after neglecting it for six months under the atmosphere of RH 65%, 50degreeC and, and the following judging standard estimated preservability over a long period of time. (Judging standard) O : an exfoliation rate is 20% or less. △: An exfoliation rate is 21~50%. x: Physical properties about thing 2 with the exfoliation rate of greater than 50%, and a zircon system oxide covering black lead fabrication object [heat resistance] After neglecting the acquired zircon system oxide covering black lead fabrication object by 600 degreeC under air atmosphere for 10 hours, the weight pace of decrease to the initial weight of a zircon system oxide covering black lead fabrication object was measured, and heat resistance was evaluated. Example 1~15 Zirconium tetraalkoxide, beta-Diketone, and isopropyl alcohol of the specified quantity shown in the 1st table were supplied to the separable flask, and the alcohol solution of Zirconium tetraalkoxide stable by agitating by churning speed 800 rpm was obtained at room temperature for 15 hours. The specified quantity shown in the obtained alcohol solution in the 1st table carries out tetra-alkoxysilane addition, After agitating by churning speed 800 rpm at room temperature for 1 hour, the aqueous hydrochloric acid which consists of the water and chloride of the specified quantity shown in the 1st table was added, and it agitated by churning speed 800 rpm at room temperature for 1 hour, and obtained the zircon system coating constituent. Using the obtained zircon system coating constituent, based on the above-mentioned measuring method, each physical properties were measured and the result was shown in the 1st table. Subsequently, the zircon system coating constituent obtained in the decompression container is supplied, After the cylindrical black lead fabrication object (diameter =20M, height =20+n+n) cleaned ultrasonically with acetone was immersed into the above-mentioned zircon system coating constituent, the inside of a decompression container was decompressed to 5 Torr, and the above-mentioned black lead fabrication inside of the body was impregnated in the zircon system coating constituent. Next, the inside of a decompression container was returned to normal pressure, the black lead fabrication object was taken out, and the zircon system coating constituent impregnating black lead fabrication object was acquired. After carrying out natural seasoning of the acquired zircon system coating constituent impregnating black lead fabrication object at room temperature for 24 hours, 100 degrees dried within the heating container for C or 24 hours, and also 1500 degrees was processed under a nitrogen atmosphere for C or 1 hour, and the zircon system oxide covering black lead fabrication object was acquired. Using the acquired zircon system oxide covering black lead fabrication object, based on the above-mentioned measuring method, the weight pace of decrease was measured and the result was shown in the 1st table. Example 16 The amount of addition of isopropyl alcohol was changed, and also the zircon system coating constituent was obtained like Example 1 as shown in the 1st table. The zircon powder (average particle diameter of 1 micrometer) of the specified quantity shown in the 1st table was added to the obtained zircon system coating constituent, and it agitated by churning speed 11000rp at room temperature for 1 hour, and obtained the zircon powder content zircon system coating constituent. Using the obtained zircon powder content zircon system coating constituent, based on the above-mentioned measuring method, each physical properties were measured and the result was shown in the 1st table. The zircon system oxide covering black lead fabrication object was acquired like Example 1 using the above-mentioned zircon powder content zircon system coating constituent. Using the acquired zircon system oxide covering black lead fabrication object, based on the above-mentioned measuring method, the weight pace of decrease was measured and the result was shown in the 1st table. (Following space) Comparative example 1~8 The amount of addition of the component in a constituent was changed, and also the zircon system coating constituent was obtained like Example 1 as shown in the 2nd table. Using the obtained zircon system coating constituent, based on the above-mentioned measuring method, each physical properties were measured and the result was shown in the 2nd table. ' The zircon system oxide covering black lead fabrication object was acquired like Example 1 using the above-mentioned zircon system coating constituent. Using the acquired zircon system oxide covering black lead fabrication object, based on the above-mentioned measuring method, the weight pace of decrease was measured and the result was shown in the 2nd table. Comparative example 9 The amount of addition of zircon powder was changed, and also the zircon powder content zircon system coating constituent was obtained like Example 15 as shown in the 2nd table. Using the obtained zircon powder content zircon system coating constituent, based on the above-mentioned measuring method, each physical properties were measured and the result was shown in the 2nd table. The zircon system oxide covering black lead fabrication object was acquired like Example 1 using the above-mentioned zircon powder content zircon system coating constituent. Using the acquired zircon system oxide covering black lead fabrication object, based on the above-mentioned measuring method, the weight pace of decrease was measured and the result was shown in the 2nd table. (Following space) Special rowing" L Momentum It was 3.5wt%, when the black lead fabrication object same with having used in Example 1 was used and the weight pace of decrease was measured based on the above-mentioned measuring method. Business @ 1.1 The zircon system coating constituent was changed into the water dispersion (catalyst transformation shrine make, a brand name; Katha Lloyd AS-3) of alumina colloid of 7 % of the weight of alumina concentration, and also the alumina colloid impregnating black lead fabrication object was acquired like Example 1. After carrying out natural seasoning of the acquired alumina colloid impregnating black lead fabrication object at room temperature for 24 hours, within the heating container, 150 degrees dried for C or 1 hour, and it acquired the alumina covering black lead fabrication object. It was 3.1wt% when the weight pace of decrease was measured based on the above-mentioned measuring method using the acquired alumina covering black lead fabrication object. Comparative example 12 The zircon system coating constituent was changed into the alcoholic dispersion liquid (catalyst transformation shrine make, brand name;03CAL) of silica colloid of 30 % of the weight of silica concentration, and also the silica colloid impregnating black lead fabrication object was acquired like Example 1. After carrying out natural seasoning of the acquired silica colloid impregnating black lead fabrication object at room temperature for 24 hours, within the heating container, 150 degrees dried for C or 1 hour, and it acquired the silica covering black lead fabrication object. It was 2.9wt% when the weight pace of decrease was measured based on the above-mentioned measuring method using the acquired silica covering black lead fabrication object. (EFFECT OF THE INVENTION) Since the composition of the zircon system coating constituent of the present invention is as having described above and it consists of a specific quantity of Zirconium tetraalkoxide, tetra-alkoxysilane, beta-Diketone, an organic solvent, and water, Coating can be done easily, and preservation is possible for a long period of time, and the coat obtained from the above-mentioned zircon system coating constituent is excellent in initial adhesion nature, boiling water resistance, and acid resistance. The above-mentioned zircon system coating constituent is used suitably for covering of metal, a plastic, wood, paper, cement, black lead, etc. In the manufacturing method of the zircon system oxide covering black lead fabrication object of present invention 2, since the above-mentioned zircon system coating constituent is used, the zircon system oxide covering black lead fabrication object in which the black lead fabrication object with which the zircon system oxide was covered was acquired by being obtained easily is excellent in heat resistance. The above-mentioned zircon system oxide covering black lead fabrication object is used suitably for the crucible for the metal dissolution, the jig for calcination, etc.